Water Molecule Structure

Water's molecular vibrations and absorptions

Water's lone pairs
Water electronic structure
Water dimer
Water models
Water reactivity

Water molecules i are tiny and V-shaped with molecular formula H2O a and molecular diameter about
2.75 Å.g In the liquid state, in spite of 80% of the electrons being concerned with bonding, the three
atoms do not stay together as the hydrogen atoms are constantly exchanging between water
molecules due to protonation/deprotonation processes. Both acids and bases catalyze this exchange
and even when at its slowest (at pH 7), the average time for the atoms in an H2O molecule to stay
together is only about a millisecond. As this brief period is, however, much longer than the
timescales encountered during investigations into water's hydrogen bonding or hydration properties,
water is usually treated as a permanent structure.

Water molecules (H2O) are symmetric (point group C2ν) with two mirror planes of symmetry and a 2-
fold rotation axis. The hydrogen atoms may possess parallel or antiparallel nuclear spin.h The water
molecule consists of two light atoms (H) and a relatively heavy atom (O). The approximately 16-fold
difference in mass gives rise to its ease of rotation and the significant relative movements of the
hydrogen nuclei, which are in constant and significant relative movement.

Note. This cartoon of water does not represent its actual outline, which is more rotund (see below).
Water's lone pairs?
The water molecule is often described in school and undergraduate textbooks of as having four,
approximately tetrahedrally arranged, sp3-hybridized electron pairs, two of which are associated with
hydrogen atoms leaving the two remaining lone pairs. In a perfect tetrahedral arrangement the bond-
bond, bond-lone pair and lone pair-lone pair angles would all be 109.47° and such tetrahedral
bonding patterns are found in condensed phases such as hexagonal ice.

Ab initio calculations on isolated molecules, however, do not confirm the presence of significant
directed electron density where lone pairs are expected. The negative charge is more evenly smeared
out along the line between where these lone pairs would have been expected, and lies closer to the
center of the O-atom than the centers of positive charge on the hydrogen atoms (as left).
Early 5-point molecular models, with explicit negative charge where the lone pairs are purported to
be, fared poorly in describing hydrogen bonding, but more recent models show some promise.
Although there is no apparent consensus of opinion [116], such descriptions of substantial sp3-
hybridized lone pairs in the isolated water molecule should perhaps be avoided [117], as an sp2-
hybridized structure (plus a pz orbital) is indicated. This rationalizes the formation of (almost planar)
trigonal hydrogen bonding that can be found around some restricted sites in the hydration of
proteins and where the numbers of hydrogen bond donors and acceptors are unequal.

Note that the average electron density around the oxygen atom is about 10x that around the hydrogen
atoms.
 The approximate shape and charge distribution of water

The electron density distribution for water is shown above right with some higher density contours
around the oxygen atom omitted for clarity. The polarizability of the molecule is almost isotropic,
centered around the O-atom (1.4146 Å3) with only small polarizabilities centered on the H-atoms
(0.0836 Å3) [736]. Parameters using ab initio calculations with the 6-31G** basis set are shown
right.j For an isolated H216O, H217O or H218O molecule, the more exact calculated O-H length is
0.957854 Å and the H-O-H angle is 104.500° (D216O, 0.957835 Å, 104.490°) [836]. The charge
distribution depends significantly on the atomic geometry and the method for its calculation but is
likely to be about -0.7e on the O-atom (with the equal but opposite positive charge equally divided
between the H-atoms) for the isolated molecule [778].d The experimental values for gaseous water
molecule are O-H length 0.95718 Å, H-O-H angle 104.474° [64].e

These values are not maintained in liquid water, where ab initio (O-H length 0.991 Å, H-O-H angle
105.5° [90]) and diffraction studies (O-H length 1.01 Å, O-D length 0.98 Å [1485]; O-H length 0.990
Å, O-D length 0.985 Å [1884]; O-D length 0.970 Å, D-O-D angle 106° [91])f suggest slightly greater
values, which are caused by the hydrogen bonding weakening the covalent bonding and reducing the
repulsion between the electron orbitals. These bond lengths and angles are likely to change, due to
polarization shifts, in different hydrogen-bonded environments and when the water molecules are
bound to solutes and ions. Commonly used molecular models use O-H lengths of between 0.957 Å
and 1.00 Å and H-O-H angles of 104.52° to 109.5°. [Back to Top ]

Water electronic structure

The electronic structure has been proposed as
1sO2.00 2sO1.82 2pxO1.50 2pzO1.12 2pyO2.00 1sH10.78 1sH20.78 [71], however it now appears that the 2s orbital
may be effectively unhybridized with the bond angle expanded from the (then) expected angle of 90°
due to the steric and ionic repulsion between the partially-positively charged hydrogen atoms (as
proposed by Pauling over 50 years ago [99]). The molecular orbitals of water,
(1a1)2(2a1)2(1b2)2(3a1)2(1b1)2, are shown on another page.
Shown opposite is the electrostatic potential associated with the water structure. Although the lone
pairs of electrons do not appear to give distinct directed electron density in isolated molecules, there
are minima in the electrostatic potential in approximately the expected positions.

Van der Waals radii [206]

The mean van der Waals diameter of water has been reported as identical with that of isoelectronic
neon (2.82 Å) [112]. Molecular model values and intermediate peak radial distribution data indicates
however that it is somewhat greater (~3.2Å). The molecule is clearly not spherical, however, with
about a ±5% variation in van der Waals diameter dependent on the axis chosen; approximately
tetrahedrally placed slight indentations being apparent opposite the (putative) electron pairs. [Back to
Top ]
Water dimer
Much effort has been expended on the structure of small isolated water clusters. Typically, in the
ambient atmosphere there is over one water dimer for every thousand free water molecules rising to
about one in twenty in steam. The equilibrium constant for dimer formation
(H2O)2(g) → 2H2O(g)
−1
is 0.0501 bar at 298.15 K [2052]. The thermochemical properties of the dimer have been
determined [2052].

The most energetically favorable water dimer is shown right using ab initio calculations with the 6-
31G** basis set.j It is also shown below with a section through the electron density distribution (high
densities around the oxygen atoms have been omitted for clarity). This shows the tetrahedralityb of
the bonding in spite of the lack of clearly seen lone pair electrons; although a small amount of
distortion along the hydrogen bond can be seen. This tetrahedrality is primarily caused by
electrostatic effects (that is, repulsion between the positively charged non-bonded hydrogen atoms)
rather than the presence of tetrahedrally placed lone pair electrons. The hydrogen-bonded proton has
reduced electron density relative to the other protons [222]. Note that, even at temperatures as low as
a few kelvin, there are considerable oscillations (< ps) in the hydrogen bond length and angles [591].
The potential energy surface [1668] and wagging vibration [1743] of the water dimer have been
described and molecular orbitals of the water dimer are shown on another page.
R = 2.976 (+0.000, -0.030) Å, α = 6 ± 20°, β = 57 ± 10° [648]; α is the donor angle and β is the
acceptor angle. The dimer (with slightly different geometry) dipole moment is 2.6 D [704]. Although
β is close to as expected if the lone pair electrons were tetrahedrally placed (= 109.47°/2), the energy
minimum (~21 kJ mol-1) is broad and extends towards β = 0°.
It has been noted that dimers of more distant water molecules (~1 nm) show synchronous behavior
due to their interacting electric fields [2086].
[Back to Top ]
Water models
Simplified models for the water molecule have been developed to agree with particular physical
properties (for example, agreement with the critical parameters) but they are not robust and resultant
data are often very sensitive to the precise model parameters [206]. Models are still being developed
and are generally more complex than earlier but they still appear to have poor predictive value
outside the conditions and physical parameters for which they were developed. [Back to Top ]
Water reactivity
Although not often perceived as such, water is a very reactive molecule available at a high
concentration. This reactivity, however, is greatly moderated at ambient temperatures due to the
extensive hydrogen bonding. Water molecules each possess a strongly nucleophilic oxygen atom that
enables many of life‘s reactions, as well as dissociating to produce reactive hydrogen and hydroxide
ions. Reduction of the hydrogen bonding at high temperatures, or due to electro-magnetic fields,
results in greater reactivity of the water molecules. [Back to Top ]

Footnotes

a
Water's composition (two parts hydrogen to one part oxygen) was discovered by the London
scientist Henry Cavendish (1731-1810) in about 1781. He reported his findings in terms of
phlogiston (later the gas he made was proven to be hydrogen) and dephlogisticated air (later this was
proven to be oxygen). Cavendish died (1810) in his Laboratory just 30 minutes' walk from the
present site of London South Bank University.
It has been suggested that H1.5O may better reflect the formula at very small (attosecond) timescales
when some of the H-atoms appear invisible to neutron and electron interaction [515]. The
experimental results have since been questioned [630] and described as erroneous [796], but have
been more recently confirmed and thought due to a failure of the Born-Oppenheimer approximation
(this assumes that the electronic motion and the nuclear motion in molecules can be separated)
[1134]. Thus the formula H1.5O is incorrect but such suggestions do, however, add support to the
view that observations concerning the structure of water should be tempered by the timescale used.
[Back]
b
The tetrahedral angle is 180-cos-1(1/3)°; 109.47122° = 109° 28' 16.39". Tetrahedrality (q, the

orientational order parameter) may be defined as , where ψjk is the

angle formed by lines drawn between the oxygen atoms of the four nearest and hydrogen-bonded
water molecules [169]. It equals unity for perfectly tetrahedral bonding (where cos(φjk) = -1/3) and
averages zero (±0.5 SD) for random arrangements, with a minimum value of -3. The density order
parameter is described elsewhere. [Back]
c
ortho-H2O rotates in its ground state with energy 23.79 cm-1 [1150]. [Back]

d
The charge on the hydrogen atoms across the periodic table are shown opposite [820]. The
hydrogen atom charges are blue and the charges on the other atoms are indicated red. [Back]
e
The actual values depend on the vibrational state of the molecule with even values of 180° being
attainable during high order bend vibrations (v2 >= 7, λ < 900 nm) for the H-O-H angle [860].
Vibrations are asymmetric around the mean positions. In the ground state, the bond angle (104.5°) is
much closer to the tetrahedral angle than that of the other Group VI hydrides, H2S (92.1°), H2Se
(91°) or H2Te (89°). [Back]
f
The H-O-H angle and O-H bond length in ice Ih are reported as 106.6°±1.5° and 0.985 Å [717]
respectively, whereas recent modeling gives H-O-H angle values of 108.4°±0.2° for ice Ih and
106.3°±4.9° for water [1028]. [Back]
g
The atomic diameter can be determined from interpolation of the effective ionic radii of the
isoelectronic ions (from crystal data) of O2- (2.80 Å), OH- (2.74 Å) and H3O+ (2.76 Å) [1167].
Coincidentally, this diameter is similar to the length of a hydrogen bond. The water molecule (bond
length 0.96 Å) is smaller than ammonia (bond length 1.01 Å) or methane (bond length 1.09 Å), with
only H2 (bond length 0.74 Å) and HF (bond length 0.92 Å) being smaller molecules. [Back]
h
As is found in molecular hydrogen (H2), the hydrogen atoms in water (H2O) may possess parallel
(paramagnetic ortho-H2O, magnetic moment = 1; the high spin state with three symmetric spin
states +1 , 0 , -1; this spin state always rotates with the lowest state 23.794352 cm-1 H216O, [607c],
23.773510 cm-1 H217O [607a] or 23.754902 cm-1 H218O [607a]) or antiparallel (nonmagnetic para-
H2O, magnetic moment = 0; the low spin state with one antisymmetric spin state 0; some of these
will not be rotating even at room temperature) nuclear spin. The equilibrium ratio of these nuclear
spin states in H2O is all para at zero Kelvin, where the molecules have no rotational spin in their
ground state, shifting to the most stable ratio [1694] of 3:1 ortho:para at less cold temperatures (>50
K);c the equilibrium taking months to establish itself in ice (or gas) and nearly an hour in ambient
water [410]. It is now thought that the ratio lies far from equilibrium and much closer to 1:1 in liquid
water due to hydrogen bond formation [2076]. This means that liquid H2O effectively consists of a
mixture of non-identical molecules and the properties of pure liquid ortho-H2O or para-H2O are
unknown. The differences in the properties of these two forms of water are expected to be greater in
an electric field [1186], which may be imposed externally, from surfaces or from water clustering
itself. Many materials preferentially adsorb para-H2O due to its non-rotation ground state [410, 835].
The apparent difference in energy between the two states is a significant 1-2 kJ mol-1, far greater than
expected from spin-spin interactions (< μJ mol-1) [835]. It has been suggested that structural
rearrangements may be induced by ortho-H2O : para-H2O conversion [1430], as it is possible that
hydrogen bonds between para-H2O, possessing no ground state spin, are stronger and last longer
than hydrogen bonds between ortho-H2O [1150]. It is thus possible that ortho-H2O and para-H2O
form separate hydrogen bonded clusters [1150] with para-H2O being preferred in the low density
tetrahedrally coordinated clusters and ortho-H2O being preferred in the high density clusters [2070],
where their rotation is more easily accomodated.

Due to deuterium's nuclear spin of 1 (compare 1/2 for H's spin; ortho D2O has two spin
states 2 and 0; para D2O has one spin state 1), the lowest energy form of D2O is ortho. D2O converts
to a 2:1 ortho:para ratio at higher temperatures. The difference in energy between the
lowest ortho state ant the lowest para state is 12.1170191 cm-1 (D216O), 12.098600 cm-1 (D217O) and
12.082026 cm-1 (D218O) [607d].

HDO, having non-equivalent hydrogen atoms, does not possess an ortho/para distinction. T2O
behaves similarly to H2O as tritium also possesses a nuclear spin of 1/2. [Back]
i
Liquid water consists of a mixture of molecules [1377] and ions, including H2O, HDO, H3O+ and
OH-. A 'standard' water (Vienna Standard Mean Ocean Water) has been proposed. 'Pure liquid water',
meaning consisting of just H2O molecules, only exists in computer simulations. Even 'just H2O'
consists of a mixture of 'ortho' and 'para' forms. Avoiding this complexity, 'water' is normally taken
to mean H2O molecules, without consideration over its magnetic state. H2O is also known as 'light
water' with D2O being heavy water (D2O density = 111% H2O density, 25 °C) and T2O being super
heavy water (T2O density = 122% H2O density, 25 °C). The properties of H2O, D2O and T2O
are different. Even though the amount of deuterium in commonly-found water is low (~16 mM) the
properties of such water are different to water containing protium (1H) only [2063]. [Back]

j
More exact parameters are given in the text. These parameters are given mainly for comparison
with the hydrogen andhydroxide ions. [Back]

Source:http://www1.lsbu.ac.uk/water/molecule.html#bi